Note: Descriptions are shown in the official language in which they were submitted.
~Z~72
This invention relates to synthetic liquid wax
esters of the jujube oil type based on long chain alkenols
and alkenoic acids which are free from glycerol and/or
glycerol derivatives.
Natural jujube oil is obtained from the fruits
of different desert plants belonging to the family of
Buxacest which have their homes inter aria in California
and Mexico. Jujube oil is not a fatty oil in the usual sense,
i.e. it is not an ester of glycerol with fatty acids, but
rather has the chemical construction of a liquid wax formed
from esters of singly unsaturated straight chain alcohols
and acids with chain length maxima of 20 to 22 carbon atoms.
The cosmetic industry has increasing interest
in liquid waxes of the jujube type of which, however, there
is at present only a very small availability of varying
quality, for example with frequently insufficient cloud
points, corresponding to the mixed source from wild plants,
since the small amount of cultivation in plantations still
does not yield any profits.
The properties of jujube oil are unusual and
differ strongly from those of fatty oils; in spite of the
unsaturated bonding in both ester components, the oil is
not rancid; the decomposition point lies at about 300C;
the oil can be kept unchanged for many years; the compute-
ability with the skin and with internal distribution is very
good; with the oil not being digestible.
Only sperm oil from the forward cavities of the
sperm whale which contains in addition to long chain liquid
waxes about 30% of fatty acid esters of glycerol, has in
part similarly valuable properties, but will no longer be
conveniently available in the future in significant amounts.
A synthesis of jujube oil with costs worth advocating has
not hitherto been possible.
The object of the present invention is to
provide a substitute for natural jujube oil from raw materials
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obtainable easily in sufficient amounts, which exhibits the
demanding property profile of the natural products.
In accordance with the invention, this object is
achieved with a synthetic liquid wax ester of the jujube oil
S type, consisting of an ester mixture obtained from sub Stan-
tidally equivalent amounts of an unsaturated carboxylic acid
component (a) and an unsaturated alcohol component (b).
In this ester mixture according to the invention,
the acid component (a) consists of a mixture off
Sal) at least one of the following amounts of straight-
chained fatty acids:
5 to 95% of singly-unsaturated C22 fatty acids,
0 to 10% of singly-unsaturated C20 fatty acids,
0 to 60% of singly-unsaturated C18 fatty acids,
0 to 25% of doubly unsaturated C18 fatty acids, and
0 to 8% of triple unsaturated C18 fatty acids;
(a) 0 to 25% of addition products of acrylic acids on
conjugated doubly unsaturated fatty acids; and
(a) 0 to 25% of dimerised fatty acids.
In the ester mixture according to the invention,
the alcohol component consists of:
0 to 10% of unsaturated C12 fatty alcohols
0 to 15% of unsaturated C14 fatty alcohols,
0 to 40% of unsaturated C16 fatty alcohols,
50 to 95% of unsaturated C18 fatty alcohols,
0 to 10% of unsaturated C20 fatty alcohols, and
0 to 10% of unsaturated C22 fatty alcohols,
all the above percentages being given by weight.
Of course, the respective amounts of acids and
alcohols used as components (a) and (b) are selected to
total 100% in each case.
The unsaturated alcohols used as component (b) in
the liquid wax ester according to the invention, consist,
except for unavoidably occurring impurities, of singly
5~;172
unsaturated straight chain primary alcohols which are produced
by high pressure hydrogenation of unsaturated fatty acids.
An anoint of octadecen-l-ol must always be present in
admixture a balance amount of primary alcohols. The position
of the double bonding, in these unsaturated alcohol can
vary depending on the starting materials used in the hydra-
genation. As C14-, C16- and Calculus, use can preferably
be made of tetradecen-l-ol, hexa-decen-l-ol and eicosen-l-ol.
Preferably, use will be made of Calculus in amounts of
2 to 15% by weight, and of Calculus in amounts of 2 to
40%.
The unsaturated carboxylic acid component (a)
may exclusively consist of straight-chained monocarboxylic
acids of group (at), or additionally of acids of groups
(a) and/or (a).
The mono-unsaturated Kissed (docosenic acid) of
group (at) is always provided with isomers having position of double
bonds at various places. Amongst these Kissed Swiss-
docosenic acid (13c--C22O1), also known as eruacaic acid, is
an essential component. 9-Cis-eicosenic acid (9c-C20:1) and
9-cis-octadecenic acid (9c-C18:1) are the most common keenest-
tent respectively of the mono-unsaturated C20-fatty acids
and the unsaturated C18-fatty acids. The usual constituents
of group (a) as well as groups (a) and (a) serve especial-
lye for the regulation and variation of important properties
such as the iodine number, the viscosity or the cloud point.
Swiss-, 12-cis-octadienlc acid (9c, 12c-C18:2) and Swiss-,
Swiss-, Swiss octadecadienic acid (9c, 12c~ 15c-C18:3) and
likewise, however, -their isomers with other positions of
double bonds, can serve especially as doubly unsaturated
C18 fatty acid and as triple unsaturated acid respectively.
Impurities, especially saturated alcohols and
saturated carboxylic acid in amounts of up to I by weight
according to the choice of commercial unsaturated alcohols
and the carboxylic acids are not usually avoidable, but
are not harmful.
C21-Dicarboxylic acids which are obtained by
Diels-Alder addition of acrylic acid to conjugated double
bonding especially of linoleic acid can be present as
component from group (a) in amounts of O to 25%. The main
constituents of the addition products are the 6-carboxy-4-
hexyl-2-cyclohexene-1-octanoic acid of the formula
- pa -
I
H3C - (SHEA (SHEA COO
COO
and the 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid
of the formula
H3C - (SHEA (SHEA COO
HOOT
BY Ward et at: J.Am.Oil Chem.Soc. Vow 52 Noah (1975)
p.219-224). The so-called dim Eric fatty acids, namely
the condensation products of fatty acids obtained according
to for example EYE. Prude: Fatty Acids, Copyright 1979 by
the American Oil Chemists Society, by alkali catalyzed
treatment of specific fatty acids can be present as come
potent of group (a). The main components are cyclic,
monocyclic and bicyclic acids of the types
H3C - (SHEA OH (SHEA COO
H3C (SHEA OH = C (SHEA
COO COO
(SHEA (SHEA
- (SHEA COO (SHEA COO
OH = OH (SHEA OH
SHEA H3C-(CH2)4
SHEA (SUE
Ho
So
in addition to which further constituents, among which are
small amounts ox trimerisation products as well as unchanged
and isomerised fatty acids are present.
The synthetic liquid wax esters are preferably
neutral esters with low acid number in the region of 0 to
5 and low hydroxyl number in the region of 0 to 10.
If desired, however, esters with contents of
carboxyl or hydroxyl groups can be produced by small vane-
lion of the equivalency of the carboxyl groups and the
hydroxyl groups in components (a) and (b). Insofar as an
excess of alcohols is appropriate in the esterification,
the excess of hydroxyl groups can be esterified after the
esterification by reaction with for example acetic ashy-
drive, so that, then, acutely residues are contained in
the product in amounts of 0 to 5% by weight.
The preparation of the synthetic liquid wax ester
takes place by esterification of mixtures of acid
components with mixtures of components (b) according
to procedures known as such. Components (a) and (b) can be
employed in equivalent amounts, related to the content of
carboxyl and hydroxyl groups, or initially contain an ox-
cuss of a component in order to accelerate the esterifica-
lion. Unstirred starting materials can be distilled
off after the reaction or removed by refining with acids
or bases or remain in the product as acutely derivatives as
a result of the indicated reaction with acetic android.
The usual esterification catalysts, preferably
zinc salts such as zinc acetate or organic titanic acid
derivatives such as tetrabutyltitanate are used as catalysts
in amounts of 0.05 to 2% by weight related to the weight
of the starting material. The reaction is carried out at
temperatures in the range of 120 to 200C, preferably at
140 to 160C, with exclusion of oxygen, preferably in
nitrogen atmosphere. For accelerated removal of the react
lion water, a carrier means, for example zillion can be
5~!7~Z
added After separation off of the calculated amount of
water, the optionally added carrier means and unesterified
starting materials, insofar as neutral esters are produced,
is removed and refined in the usual manner, deodorized,
bleached and dried.
The synthetic wax esters surprising match the.
exacting property profile which is typical of those esters
present in nature, in spite of varying chemical compost-
lion up to that which can be confused with product charges
related thereto, and exceed the natural products in Essex-
trial and characteristic properties. Advantages are yielded
especially by the high iodine number, the low peroxide
number, low viscosity and low cloud points. It is special-
lye stressed that the products according to the invention
do not become rancid but possess good skin compatibility
and skin care properties and are so atomic, with LD50-
values of above 20 g/kg, that they can serve as a constituent
of diet foods - since they are poorly digested and of only
small nutritional value. The molecular constitution is
unusually stable with a temperature resistance above 300C,
large resistance to acid even at high temperatures as a
result of very low peroxide numbers and high resistance
to enzymatic vulnerability in the presence of water or hydra-
loses. The wax esters do not contain any hydrocarbons
steroids, strolls, free alcohols or acids or other act
companying material which, from the physiological and toxin
ecological point of view, could be serious for example as
allergens or sources of eczema. The products can, on the
one hand, be compared fully to the characteristic properties
of natural jujube oil or even to especially expensive
batches, and on the other hand, these properties are so
variable that, for selected usages, the properties are
better suited than the natural product. The natural product
is surpassed especially with reference to the iodine number,
low peroxide number, low viscosity and the cloud points
I
lying lower, down to 10C. In contrast to a synthetic
symmetric ester formed from mono-unsaturated Colloquial
and mono-unsaturated C20 fatty acid, which is nut home-
generous below 18C, the wax ester according to the invent
lion louses shows advantages in the cloud points which
lie lower, down to 10C. The product according to the
invention can therefore replace natural jujube oil in all
preparations, just like natural sperm oil, there existing
in contrast the advantage of freedom of lipids, that is
glycerol esters.
The liquid wax ester can be for example base or
auxiliary material in cosmetic formulations such as creams,
lotions, skin and hair oils, shampoos, sun-screening agents,
lip salves, deodorants and soaps, for dietetic preparations,
as well as vehicles in pharmaceutical preparations. They
can be worked together with vegetable, animal and synthetic
oils, fats and waxes, for example to very stable W/O or
O/W emulsions. They possess an outstanding spreading pro-
petty and axe therefore employed as such or as components
of blended ointment systems. They can furthermore be
modified chemically in numerous ways and be reacted to
valuable ongoing products for technical uses, perhaps in
machining or pressing or roller working. Waxes of semi
solid to solid consistency can be produced by hydrogen-
lion, high-pressure lubricants can be produced by addition
of Selfware, and intermediate products of different types
can be produced by epoxidation, chlorination or isomerism-
lion.
In order to increase further the stability of the
products against oxidative attack, unobjectionable anti-
oxidants such as 2(3)-tert.-butyl-4-hydroxyanisole or
-Tulane (TBHA or BUT) can be dissolved therein in amounts
of 0 to I by weight. Thus stabilized products are us-
changed in peroxide number, in color and sensory proper-
ties after 200 hours gazing with air in a finely bubbled
stream at 90C.
A further subject of the invention is the use of
the products as substitutes for jujube oil.
The invention will be further understood by
reference -to the following non-restrictive examples.
1 Mole of a mixture of acids with the composition
indicated under S 1 to S 6 with 0.9 to 1.1 mole of a mix-
lure of alcohols of the composition All to A 3 is heated
under nitrogen to 140 to 160C in a heated three-necked
flask which is provided with thermometer, stirrer, reflex
condenser and water separator, while under addition of
100 ml of dry zillion as carrier material and 0.1% by weight
zinc acetate, while the carrier means removes the reaction
water from the mixture as it is undergoing reflex.
The acid mixtures are constituted as follows
(amounts in % by weight), with the acids having is-
configuration and being in each case predominantly an
item indicated in the description:
C18:1C18:2 C18:3 C20:1 C22:1 * ** By-
products
S 1 1 0.1 0.3 2 95 - - 1.6
S 250 15 3 4 24 2 - 2
S 370 8 2 1 18
S 460 10 8 2 14 - 3 3
S 550 15 4 3 1511 - 2
S 650 12 3 2 1510 5 3
The alcohol mixtures are composed as follows (% by weight)
C14:1 C16:1 C18:1 C20:1 By-products
A 1 3 5 85 4 3
A 2 4 13 80 2
A 3 6 17 74 1 2
* = C21-Dicarboxylic acids of components a
** = dim Eric fatty acids of components a
- 8 -
Aster six hours on average, the calculated amount
of water is obtained. Carrier material and excess of reactants
are distilled off in vacua. The crude ester is extracted
with water, deacidified by means of bicarbonate or soda soul-
lion, if necessary acetylated with acetic android in an amount equivalent to the hydroxyl number of the crude ester,
washed neutral with water, decolourized with active charcoal
and/or active earth, deodorized and dried. The yields of
ester are approximately quantitative, related to the combo-
lo newts employed in excess.
The esters obtained and their properties are
listed in the following Table.
In the Table, Slyly and the compositions which
follow signify neutral esters formed of the indicated come
pennants. Viscosities are measured in mm2/sec.
so
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